CN110092379A - It is a kind of using biomass as the method and application of raw material one-step synthesis sulfonation active carbon - Google Patents
It is a kind of using biomass as the method and application of raw material one-step synthesis sulfonation active carbon Download PDFInfo
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- CN110092379A CN110092379A CN201910293034.7A CN201910293034A CN110092379A CN 110092379 A CN110092379 A CN 110092379A CN 201910293034 A CN201910293034 A CN 201910293034A CN 110092379 A CN110092379 A CN 110092379A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Abstract
The present invention provides a kind of using biomass as the method and application of raw material one-step synthesis sulfonation active carbon: first by biomass material mixing acid dip, and impregnation increment is be saturated impregnation increment 50%~100%, it is subsequently placed in 110 DEG C~500 DEG C of condition, 2~12h is reacted under certain atmosphere, when environment temperature≤300 DEG C, it can also be directly exposed under air atmosphere and react, be cooled to room temperature, cleaning solution is washed with distilled water to as neutrality, finally the sulfonation active carbon after washing is dried；Application of the sulfonation active carbon in sewage treatment: for removing heavy metal ion and organic pollutant in sewage.The present invention is using abandoned biomass as raw material, raw material sources are wide, it is at low cost, and one step complete biomass material carbonization, activation and sulfonation process, compared to the sulfonation active carbon process of multistep processes preparation, the obvious destruction for weakening p-sulfonic acid base and active carbon cellular structure, significantly improves the specific surface area and sulfonic group content of sulfonation active carbon.
Description
Technical field
The invention belongs to biomass recycling use technical fields, further relate to active carbon processing technique field, and in particular to
It is a kind of using biomass as the method and application of raw material one-step synthesis sulfonation active carbon.
Background technique
Biomass source is abundant, specifically includes that the agricultural products such as the stalk, shell, fruit stone generated in agricultural production process
And waste；Forestry products and the wastes such as trees, branch, sawdust during production of forestry；Animal husbandry, aquaculture generate
The animal wastes such as cow dung, sheep dung and chicken manure；The wastes such as furfural dregs, discarded wrapping paper in industrial processes.However, biological
Matter resource is not effectively utilized, except on a small quantity in addition to fuel, feed, papermaking and fertilizer, it is most by on-site incineration,
Burying or abandoning makes its natural degradation in field.These processing methods cause resource and greatly waste and environmental problem.So
The resource utilization for realizing biomass, can alleviate environmental pollution phenomenon while creating economic value.
Organic pollutant and heavy metal are the major pollutants in sewage.Organic pollutant refer to carbohydrate,
Natural organic substance existing for the forms such as protein, amino acid and fat and certain other are biodegradable artificial synthesized
Organic substance is the pollutant of composition.Heavy metal, especially mercury, cadmium, lead, chromium etc. have significant bio-toxicity, Ta Men
Cannot be degraded by microorganisms in water body, and can only occur various forms mutually convert and disperse, enrichment process.The two not only can shadow
The existence for ringing aquatic animals and plants, can also endanger the drinking water safety of the mankind.Organic pollutant sewage removing method includes absorption, life
Object degradation, air lift, hydrolysis and photodissociation etc..The processing method of heavy metal ion sewage is generally used absorption method, with single
Adsorption treatment agent is on the high side, and adsorption effect is not highly desirable.It handles dirty organic pollutants and heavy metal is usual
It needs using different processing means and treatment process, process flow is more complicated.Organic dirt can be removed simultaneously by developing one kind
The method of dye object and heavy metal contaminants can greatly simplify the process flow of sewage, improve sewage treating efficiency.
Absorbent charcoal material is that the carbon-rich materials such as biomass, coal and high molecular material are resulting amorphous by working process
Carbon has very big specific surface area, in gas, solution inorganic or organic substance and colloidal solid etc. have good absorption
Ability.A kind of adsorbent of the absorbent charcoal material as function admirable, mainly due to it with unique surface texture properties and
Surface chemistry.The chemical property of active carbon is stablized, and high mechanical strength is acidproof, alkaline-resisting, heat-resisting, it is not soluble in water with it is organic molten
Agent can regenerate use.Organic pollutant in the adsorbable water of active carbon, is widely used in sewage treatment field.In active carbon
After surface introduces sulfonic group by sulfonating reaction, sulfonation active carbon can be made, having the same of absorption organic pollutants
When, it can be exchanged with heavy metals such as lead, mercury, cadmium, copper in water, from the efficient heavy metal removed in sewage.Therefore, sulfonation is living
Property charcoal be a kind of difunctional excellent sewage-treating agent that can remove organic pollutants and heavy metal contaminants simultaneously.
Chinese patent CN201310080712.4 disclose a kind of sulfonation wood activated charcoal prepare raw material, preparation method and
It is applied, and the raw material of this method is wood activated charcoal obtained in advance, by wood activated charcoal with 95%~98% the concentrated sulfuric acid it is anti-
It should make active carbon sulfonation.Sulfonation active carbon made from this method only can be used as the heterogeneous catalyst of ethylene oxide hydration reaction.In
State patent CN201710169764.7 discloses a kind of method that the sulfonation of biomass active carrier prepares solid acid, and this method is with work
Property charcoal be raw material, using 98% concentrated sulfuric acid be sulfonating agent preparation sulfonation active carbon.The specific surface area of active carbon made from this method
It is extremely low, it is 5~10m2/ g does not have the ability of absorption organic pollutant, is used only as the catalyst of the alkylated reaction of cresols.
Chinese patent 201310005875.6 discloses a kind of method for preparing sulfonation active carbon as raw material using pitch, and this method is made first
Standby sulfonated gilsonite, then activate sulfonated gilsonite for active carbon by activator of KOH, which can be used as electrode for capacitors
Material.Chinese patent 2018107979-22.8, which is disclosed, a kind of suitable for big partial size and adsorbs the active carbon of heavy metal ion
Preparation and regeneration method, this method obtain active carbon by sulfonation, carbonization using polyimides as raw material, which can adsorb
Heavy metal in sewage.
The preparation method of above-mentioned sulfonation active carbon needs that raw material carbonization, activation are first made active carbon, then by active carbon sulphur
Sulfonation active carbon is made in change, or first by raw material sulfonation, is then carbonized again, activates to obtain sulfonation active carbon, i.e. these sides
Method needs the preparation of active carbon and two steps of sulfonation of active carbon, and this method not only consumes energy high, time-consuming, but also if first sulphur
Change the sulfonic group that post activation is easily destroyed introducing, if sulfonation after first activating, is easily destroyed the hole of active carbon in sulfonation process
Structure causes the pore structure of active carbon to be destroyed, and specific surface area reduces, and destroys its adsorption capacity.Above-mentioned Part Methods are using drip
Green and high molecular polymer is that raw material prepares active carbon, and higher cost is not suitable for being applied to large-scale sewage treatment.In addition,
Active carbon is placed in the excessive concentrated sulfuric acid in sulfonation process and heats by the above method, again by sulfuric acid and sulfonation active carbon after reaction
Separation, can generate more spent acid.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide one kind using abandoned biomass as one step of raw material
The method for synthesizing sulfonation active carbon.The carbonization, activation of raw material prepare active carbon in this method and the sulfonation process of active carbon passes through
One step is completed, and can be shortened process route, be reduced cost.This method is using the side for being saturated dipping acid or unsaturated dipping acid
Method, it is possible to reduce sour dosage saves cost, while reducing the discharge of spent acid pollutant.
Technical solution of the present invention is summarized as follows:
A method of using biomass as raw material one-step synthesis sulfonation active carbon: first by biomass material mixing acidleach
Stain, and impregnation increment is be saturated impregnation increment 50%~100%, being subsequently placed in 110 DEG C~500 DEG C of condition (can be direct by raw material
It is placed in and rises in the environment of reaction temperature in advance, or by room temperature with certain heating rate temperature programming to reaction temperature, journey
Sequence heating rate range is no more than 15 DEG C/min), 2~12h is reacted under certain atmosphere, when environment temperature≤300 DEG C,
It can also be directly exposed under air atmosphere and react, the reaction time controls in 6~12h, is cooled to room temperature, is washed with distilled water to
Cleaning solution is neutrality, and finally the sulfonation active carbon after washing is dried；
The mixed acid is the mixed liquor of 60%~85% phosphoric acid and 80%~98% sulfuric acid, and the two mixed volume ratio is 1:
(0.5~4)；Wherein, phosphoric acid primarily serves the effect of activator, i.e., carries out reaming to biomass material, and sulfuric acid primarily serves sulphur
The effect of agent introduces sulfonic group in activated carbon surface, in addition, mixed acid can accelerate the carbonization of biomass, therefore 110
DEG C~300 DEG C within the temperature range of the preparation of active carbon, while 110 DEG C~300 DEG C cryogenic conditions still may be implemented, make biology
Charing, activation process can be completed in matter raw material in air atmosphere, and without stringent inert gas atmosphere requirement, energy consumption is lower,
It is suitble to industrialization large-scale production.
Preferably, the biomass material specifically include agricultural, forestry, animal husbandry or industrial processes biomass product and
Its waste, such as one of timber, trees branch, stalk, fruit stone, shell, excrement of animals, furfural dregs and waste paper.
Preferably, the mixed acid dipping process is using saturation dipping or unsaturated dipping, detailed process are as follows: first weigh
By the powdered biomass of a certain amount of 110 DEG C dry 12h, then mixing is added dropwise in the powdered biomass partial size < 0.85mm dropwise
Acid is sufficiently stirred simultaneously, reaches acid at this time raw until having free acid that can not be adsorbed just by biomass uniform adsorption
The saturation of substance impregnates, and mixed acid amount used is that (saturation impregnation increment is different with the property of raw material, can pass through reality for saturation impregnation increment
Test is fixed), it is unsaturation dipping when mixed acid amount used is less than saturation impregnation increment, it is specific to control sour dosage as saturation dipping
The 50%~100% of amount, and the biomass for impregnating peracid is placed into 1~4h at room temperature, make mixed acid in powdered biomass
It can be evenly dispersed；It can all be absorbed by biomass using the mixed acid that above method impregnates, therefore not need to filter, do not had
Excessive spent acid generates.
Preferably, the reaction atmosphere is one of nitrogen, argon gas, helium, vapor, carbon dioxide or a variety of.
Preferably, the drying temperature is 110 DEG C, drying time 6h.
Application of the sulfonation active carbon in sewage treatment: for removing heavy metal ion and organic pollutant in sewage.
Preferably, the heavy metal ion be specifically including but not limited to as copper, lead, zinc, iron, cobalt, nickel, manganese, cadmium, mercury,
Tungsten, molybdenum, gold, silver.
Preferably, the organic pollutant be specifically including but not limited to methylene blue, phenol, cresols, 3,4- BaP,
Pesticide residue.
Detailed description of the invention
Fig. 1 is the flow chart of the method for the present invention；
Fig. 2 is that the electronics for the sulfonation active carbon that embodiment 1 is produced using corn stover as biomass material shines；
Fig. 3 is that the electronics for the forming cylinder shape sulfonation active carbon that embodiment 2 is produced using walnut shell as biomass material shines；
Fig. 4 is that the electronics for the sulfonation active carbon that embodiment 3 is produced using sawdust as biomass material shines；
Fig. 5 is that the electronics for the sulfonation active carbon that embodiment 4 is produced using furfural dregs as biomass material shines；
Fig. 6 is that the electronics for the sulfonation active carbon that embodiment 5 is produced using cow dung as biomass material shines；
Fig. 7 is that the electronics for the sulfonation active carbon that embodiment 6 is produced using rice husk as biomass material shines；
Fig. 8 is that the electronics for the sulfonation active carbon that embodiment 7 goes out by biomass material of old newsprint shines；
Fig. 9 is the scanning electron microscope image for the sulfonation active carbon that embodiment 4 is produced using furfural dregs as biomass material.
Beneficial effects of the present invention:
(1) step of the invention realizes carbonization, activation and the sulfonation of biomass material, the sulfonation active carbon specific surface prepared
Product is 900~1600m2/ g, sulfonic group content are 0.20~0.5mmol/g, can simultaneously effective remove organic dirt in sewage
Contaminate object and heavy metal contaminants；The sulfonation active carbon is levied to the adsorption capacity of organic pollutant, Asia with methylene blue adsorption number scale
Methyl blue large amount of adsorption is higher than 85% in 170mg/g, to the clearance rate of mercury ion and lead ion, but the sulfonation active carbon not only limits
In mercury ion and lead ion can be removed, the metal ion of the polluted sources such as cadmium, chromium, copper, nickel can also be removed, passes through the sulfonation
Active carbon processing sewage greatly simplifie the treatment process of sewage, improve sewage treating efficiency, reduce sewage treatment at
This.
(2) mixed acid of the present invention is the mixed liquor of 60%~85% phosphoric acid and 80%~98% sulfuric acid, the two mixed volume
Than for 1:(0.5-4), wherein phosphoric acid primarily serves the effect of activator, i.e., carries out reaming to biomass material, and sulfuric acid mainly rises
To the effect of sulfonating agent, i.e., sulfonic group is introduced in activated carbon surface, in addition, mixed acid accelerates the dehydration carbonization of biomass material,
The carbonization and activation of raw material can be realized within the scope of 110 DEG C~300 DEG C, reaction temperature is lower, energy consumption is reduced, meanwhile, 110
DEG C~300 DEG C of cryogenic conditions, the charing of biomass material, activation process can carry out in air, without stringent indifferent gas
Body atmosphere requirements, are more suitable for industrialization large-scale production；And the impregnation increment of mixed acid is less than or equal to (the saturation leaching of saturation impregnation increment
Stain method or unsaturated infusion process), excessive spent acid is not generated, without filtering, simplifies operating procedure, meanwhile, the dosage of acid is reduced,
Cost is saved, and reduces the discharge of spent acid pollutant.
(3) for the present invention using abandoned biomass as raw material, raw material sources are wide, at low cost, and a step completes biomass material
Carbonization, activation and sulfonation process, the sulfonation active carbon process prepared compared to two-step method or three-step approach, hence it is evident that weaken p-sulfonic acid
The destruction of base and active carbon cellular structure significantly improves the specific surface area and sulfonic group content of sulfonation active carbon.
Specific embodiment
Further detailed description is done to preparation method of the invention below in conjunction with specific embodiment.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Refering to Figure of description 1-8
Embodiment 1 prepares sulfonation active carbon by biomass material of corn stover
It takes 5g in the maize straw powder (its partial size < 0.85mm) of 110 DEG C of dry 12h, is added dropwise into maize straw powder
Mixed acid, the volume ratio of sulfuric acid and phosphoric acid is 1:1 in mixed acid, and the concentration of sulfuric acid is 98%, and the concentration of phosphoric acid is 75%, is added dropwise
It is sufficiently stirred in the process, the saturation impregnation increment that 4.8g reaches corn stover is added dropwise, is then being placed at room temperature for maize straw powder
2h keeps mixed acid evenly dispersed in maize straw powder, and maize straw powder is then placed in 12h in 350 DEG C of environment, gas
Atmosphere is nitrogen atmosphere, after reaction that product is cooling, is washed with distilled water, filters, until cleaning solution is neutrality, then by product
In 110 DEG C of dry 6h, sulfonation active carbon is obtained.
Embodiment 2 prepares sulfonation active carbon by biomass material of walnut shell
It takes 5g in the walnut shell powder (its partial size < 0.85mm) of 110 DEG C of dry 12h, mixing is added dropwise into walnut shell powder
Acid, the volume ratio of sulfuric acid and phosphoric acid is 1:2 in mixed acid, and the concentration of sulfuric acid is 98%, and the concentration of phosphoric acid is 80%, and process is added dropwise
In be sufficiently stirred, mixed acid dripping quantity is 3g the 60% of impregnation increment (saturation), and walnut shell powder is then being placed at room temperature for 2h, is being made
Mixed acid is evenly dispersed in walnut shell powder, and walnut shell powder is then heated to 450 DEG C with the heating rate of 5 DEG C/min,
And 2h is kept at this temperature, and atmosphere is nitrogen atmosphere, it is after reaction that product is cooling, it is washed with distilled water, filters, until washing
Liquid is washed as neutrality, product is then obtained into sulfonation active carbon in 110 DEG C of dry 6h.
Embodiment 3 prepares sulfonation active carbon by biomass material of sawdust
It takes 5g in the sawdust (its partial size < 0.85mm) of 110 DEG C of dry 12h, mixed acid, sulphur in mixed acid is added dropwise into sawdust
The volume ratio of acid and phosphoric acid is 2:1, and the concentration of sulfuric acid is 90%, and the concentration of phosphoric acid is 85%, is sufficiently stirred during being added dropwise, and is dripped
Add 4.9g to reach the saturation impregnation increment of sawdust, sawdust is then being placed at room temperature for 4h, keeps mixed acid evenly dispersed in sawdust, connect
Sawdust is heated to 400 DEG C with the heating rate of 10 DEG C/min, and keep 5h at this temperature, atmosphere is nitrogen atmosphere, instead
It is after answering that product is cooling, it is washed with distilled water, filters, until cleaning solution is neutrality, then by product in 110 DEG C of dry 6h,
Obtain sulfonation active carbon.
Embodiment 4 prepares sulfonation active carbon by biomass material of furfural dregs
It takes 5g in the furfural dregs (its partial size < 0.85mm) of 110 DEG C of dry 12h, mixed acid, mixed acid is added dropwise into furfural dregs
The volume ratio of middle sulfuric acid and phosphoric acid is 1:3, and the concentration of sulfuric acid is 85%, and the concentration of phosphoric acid is 85%, is sufficiently stirred during being added dropwise
It mixes, mixed acid dripping quantity is 2.5g (the 50% of saturation impregnation increment), and furfural dregs are then being placed at room temperature for 3h, are making mixed acid in chaff
It is evenly dispersed in aldehyde slag, furfural dregs are then placed in 12h in 250 DEG C of environment, atmosphere is air atmosphere, will be produced after reaction
Object is cooling, is washed with distilled water, filters, until cleaning solution is neutrality, product is then obtained sulfonation activity in 110 DEG C of dry 6h
Charcoal.
Embodiment 5 prepares sulfonation active carbon by biomass material of cow dung
It takes 5g in the cow dung powder (its partial size < 0.85mm) of 110 DEG C of dry 12h, mixed acid is added dropwise into cow dung powder, mix
Closing the volume ratio of sulfuric acid and phosphoric acid in acid is 1:1, and the concentration of sulfuric acid is 98%, and the concentration of phosphoric acid is 85%, is filled during being added dropwise
Divide stirring, mixed acid dripping quantity is 3g (the 65% of saturation impregnation increment), and cow dung powder is then being placed at room temperature for 2h, is making mixed acid
It is uniformly distributed in cow dung powder, cow dung powder is then placed in 3h in 450 DEG C of environment, atmosphere is argon atmosphere, reaction knot
It is after beam that product is cooling, it is washed with distilled water, filters, until cleaning solution is neutrality, then obtain product in 110 DEG C of dry 6h
Sulfonation active carbon.
Embodiment 6 prepares sulfonation active carbon by biomass material of rice husk
It takes 5g in the rice husk powder (its partial size < 0.85mm) of 110 DEG C of dry 12h, mixed acid, mixing is added dropwise to rice husk powder
The volume ratio of sulfuric acid and phosphoric acid is 1:4 in acid, and the concentration of sulfuric acid is 98%, and the concentration of phosphoric acid is 75%, abundant during dropwise addition
Stirring, mixed acid dripping quantity are 3g (the 75% of saturation impregnation increment), and rice husk powder is then being placed at room temperature for 2h, mixed acid is made to exist
It is evenly dispersed in rice husk powder, rice husk powder is then placed in 10h in 500 DEG C of environment, atmosphere is carbon dioxide atmosphere, reaction
After product is cooling, be washed with distilled water, filter, until cleaning solution is neutrality, then obtain product in 110 DEG C of dry 6h
To sulfonation active carbon.
Embodiment 7 prepares sulfonation active carbon by biomass material of old newsprint
It takes 5g in the old newsprint powder (its partial size < 0.85mm) of 110 DEG C of dry 12h, mixed acid is added dropwise to old newsprint powder,
The volume ratio of sulfuric acid and phosphoric acid is 1:1 in mixed acid, and the concentration of sulfuric acid is 98%, and the concentration of phosphoric acid is 75%, during dropwise addition
It is sufficiently stirred, mixed acid dripping quantity is 4.9g (saturation impregnation increment), and old newsprint powder is then being placed at room temperature for 1h, is making mixed acid
It is evenly dispersed in old newsprint powder, old newsprint powder is then placed in 10h in 110 DEG C of environment, atmosphere be carbon dioxide and
The ratio between volume flow of the mixed atmosphere of argon gas, carbon dioxide and argon gas is 1:1, after reaction that product is cooling, with distillation
Then product is obtained sulfonation active carbon in 110 DEG C of dry 6h until cleaning solution is neutrality by water washing, filtering.
Characterize what embodiment 1-7 was prepared respectively by methylene blue adsorption number amount, to the clearance rate of mercury ion and lead ion
Sulfonation active carbon is shown in Table 1 to the Scavenging activities of dirty organic pollutants and heavy metal, specific performance index:
Table 1 lists the sulfonation activated carbon product characterization and performance indicator of embodiment 1-7
As shown in Table 1, the sulfonation active carbon specific surface area that the present invention prepares is 900~1600m2/ g, sulfonic group content
For 0.20~0.5mmol/g, 170mg/g is greater than to methylene blue adsorption number amount, the clearance rate of mercury ion and lead ion is higher than
85%, it can simultaneously effective remove the organic pollutant and heavy metal contaminants in sewage.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details.
Claims (8)
1. a kind of using biomass as the method for raw material one-step synthesis sulfonation active carbon, it is characterised in that: the following steps are included:
First by biomass material mixing acid dip, and impregnation increment is be saturated impregnation increment 50%~100%；
It is subsequently placed in 110 DEG C~500 DEG C of condition, 2~12h is reacted under certain atmosphere, when environment temperature≤300 DEG C,
It can also be directly exposed under air atmosphere and react, the reaction time controls in 6~12h；
It is cooled to room temperature, is washed with distilled water to cleaning solution as neutrality；
Finally the sulfonation active carbon after washing is dried；
Wherein, the mixed acid is the mixed liquor of 60%~85% phosphoric acid and 80%~98% sulfuric acid, and the two mixed volume ratio is
1:(0.5~4).
2. a kind of using biomass as the method for raw material one-step synthesis sulfonation active carbon according to claim 1, which is characterized in that
The biomass material is agricultural, forestry, animal husbandry or one of industrial processes biomass product and its waste.
3. a kind of using biomass as the method for raw material one-step synthesis sulfonation active carbon according to claim 1, which is characterized in that
The mixing acid dip detailed process: taking the powdered biomass of 110 DEG C of dry 12h, the powdered biomass partial size < 0.85mm,
Be added dropwise mixed acid thereto, be sufficiently stirred during being added dropwise, be added dropwise to the saturation impregnation increment 50% of taken powdered biomass~
After 100%, it is being placed at room temperature for 1~4h, is keeping mixed acid evenly dispersed in powdered biomass.
4. a kind of using biomass as the method for raw material one-step synthesis sulfonation active carbon according to claim 1, which is characterized in that
The reaction atmosphere is one of nitrogen, argon gas, helium, vapor, carbon dioxide or a variety of.
5. a kind of using biomass as the method for raw material one-step synthesis sulfonation active carbon according to claim 1, which is characterized in that
The drying temperature is 110 DEG C, drying time 6h.
6. a kind of application of sulfonation active carbon in sewage treatment, it is characterised in that: for removing the heavy metal ion in sewage
And organic pollutant.
7. application of the sulfonation active carbon in sewage treatment according to claim 6, which is characterized in that the heavy metal ion
It is specifically including but not limited to such as copper, lead, zinc, iron, cobalt, nickel, manganese, cadmium, mercury, tungsten, molybdenum, gold, silver.
8. application of the sulfonation active carbon in sewage treatment according to claim 6, which is characterized in that the organic pollutant
It is specifically including but not limited to methylene blue, phenol, cresols, 3,4- BaP, pesticide residue.
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